Fiber forming composition containing polymerized acrylonitrile



- i This, invention antes -tfiberv forming compositionsn More specifically: 'theinvention relates. to acrylonitrile polymers Patented July 15, 1952 FIBER FonnnNG COMPOSITION ING POLYMERIZED Acnrmmrrmm V Alfred-B. Craig,

Chemical Company, S

l tion of Delaware,

No Drawing; "Application 27519 50,"

Dayton, and Ear-1 Gluesena I kamp, Centerville, Ohio; assignors to Monsanto t.'- Mo.,'' a corpora- CONTAIN-I Serial No. 197,827

capable of being dyed E by conventional procedures especially with acid dyestuii's.

j It is well-known that polyacrylonitrile and copolymers of acrylonitrile {and other monooleflnic polymerizable monomers, areiexcellent -fiber-forming zcopolymers. The polyacrylonitrile andzcopolymers' of more than 75 per cent qacrylonitrile .andflup t0 ,25wper cent r of other polymerizable, ,monomers produce, fibers'hwith superior tensile; properties, desirable. elongation,

and excellent stability under a; widei'rang'e of physical and chemical conditions. 'Thesep'olymers are subject to inherent disabilities which greatly restrict the utility in the fabrication of general purpose fibers. For example, the fibers do not have suiiicient dye afllnity toenable-the development of satisfactory colored fibers, and

"the, limited range of colors produced by con- ;-ventional dyeing techniques arecnot-stable to laundering and dry-cleaning procedures.

The purpose of this invention is to provide a new and valuable generalpurpose fiber. A

further purpose of the inventionis to provide fiber forming acrylonitrile polymers which are dye-receptive by conventional, procedures; A

still further purpose of the invention is to provide a convenient means for modifying non-dye receptive acrylonitrile polymers and converting them into polymers with excellentdye afilnity without depreciating the properties of the fibers produced therefrom; 1

It has been found forming polymers and copolymers of the. prior art, such as polyacrylonitrile and copolymers of ,9 5 per cent of acrylonitrile and five per cent vinyl acetate may be made into dyeable form by the incorporation of substantial proportions of polymers of N-vinylimidazole.

The prior art acrylonitrile polymers which may be modified by the incorporation of polymers of N-vinylimidazole are polyacrylonitrile, and copolymers of '75 per cent or more percent acrylonitrile and up to 25 per cent of monomers, .such as vinyl'acetate'and other, vinyl esters of monocarboxylic acids having up to four carbon atoms, methyl methacrylate, and otheryalkyl methacrylates having up to four carbon" atoms inrthe alkyl radical, methyl acrylate and other alkyl acrylates having up to four carbon atoms in the alkyl groups, dimethyl fumarate and other dialkyl fumarates having up to four cari bon atoms in the alkyl groups, dimethyl maleate to newvaluable that non-dyeable fiber 9 Claims; (01. 260 -455) and other dialkyl maleates having up four "carbon;atoms "m the alkyl groups, *s'tyrenq'amethlylstyrene, and other vinyl or isopropenyl substituted aromatic hydrocarbons, vinyl chloroacetate'and other" vinyl esters of halo substituted acetic acids, vinylidene chloride, and methacrylonitrile. These polymers and copolymers are, in general, of negligible dye receptivity and therefore are not useful in the preparation of m general purpose fibers.

In the practice of "this invention polymers'of N-vinylimidazole are separately prepared "and intimately mixed with the non-dyeable acryl'oni ,trile polymers. .The resulting blends will be spinnable by conventional; methods into fibers which are receptive to acidjdyeable conventional 7 dyeing procedures.- I

The polymers of N-vinylimidazole maybe the homopolymer, or they may be 'copolymers of N-vinylimidazole and a wide variety of 'olefinic monomers copolymerizable therewith. Useful T monomers for effecting this polymerization are 2styrene, a-methylstyrene, vinyl chloride-,, vinylidene chloride, vinyl acetate, acrylonitrile; methacrylonitrile,

- acrylic acid, methacrylic, acid,

maleic-anhydridathe alkyl acrylates, jthe-alkyl methacrylates, vinyl ethers, alkyl crotonates, the alkylmaleates, the alkyl fumarates, buta- ,diene, j isoprene, and chloroprenc. Since the .copolymersof N-vinylimidazole and: acryloniv trile have good thermal stability and solvent ;re-

sistance, these copolymersare usually preferred.

' 'I'hecopolymers are added in suchproportions Lthat from two to 15 percent of the total mon- :omers in "the blended composition .is Nevinylimidazole. v The polymers and copolymers of N vinylimidazole may be prepared by mass, solution, or emulsion polymerization procedures in: the

various manners well known to the art. A D 7 ferred method of polymerization involves a re.-

action in aqueous medium in the presence of 1.; suitable dispersing agents and suitable f-ree radical producing catalysts. '45

-mers of N-vinylimidazole it has been found that In-the preparation of the-emulsion co pol ya widevariety of-emulsion stabilizing agents 1;.;.; may.bev used, but the alkali metal saltsof-formaldehyde condensed naphthalene sulfonic- -acids,

iygcessful;

rand water-soluble types as well as azo :derivaand various alkali metal salts of fatty acids and fatty acid mixtures have been unusually suc- As catalysts, various peroxides,;both oil tives may be used,

peratures. Suitable solvents for blending the i nation agg acrylonitrile polymers and the li vi iylimidazole 1opolymers are N,N-dimethy1f0rma'm'ide;-*MN di- 7455 6 methylacetamide, a-butyrolactone ethylene car 7 bonate, and N,N-dimethylmethoxyacetamide. g'

the N-vinylimidazole polymers may be blended from the copolymer of 5O'per cent of acrylonitrile by any conventional liquid or solid mixing maand 50 per cent of N-vinylimidazole. The fibers chine, for example Banbury mixers, roll mills 'were spun from each blend and were found to dough e Al hough the mix g m y be dyeable and possessing the following charactake place at; elevated temperatures; where the s .teristi cs' polymersar'e soft solids or in semiliquid-sta'te. u it is preferred to add suitable solvents or plas- WeightP'e-r Spinal-11g I s V Permit ticizers to achieve the same state at lower item- Cent Nwiny]. Solutwn grams/ Stretch B9 Elon- Goncendenier' Rates Shrinkgation These various solvents are .addedain sufiicient t v V proportions to render the mixedrsonds liquid or 15 All' ofthese fibers were found to exhaust both Plastic, in which conditions. r e l l sami mee two pen cent and 'ten' per cent dyebaths mixing of the solid component's"is moreleasily 1 efi'ected. In general, from 50 to 90 per cent of claims.

the solvent will produce the desired semiliquid' vew f w c m is: V V v or soft 501m State 1. A dyeablefiber forming composition com- Premium! lzleldedifpolywrs prising a'blendiof a polymer ofF'at least '75 per thgquantltyiof eachcomponentrwmidepend'upon "cent of acrylonit'rile *and' a polym'er ofN-vinflv th imidazole; thecomponents-of theblend'beingso "final composltmngnqf-upon e-pmpm proportioned as toaprovide'from two to ten-per Z'Ifhe invention is defined by the following 'Nwmyu'midamle N'vmyumdazdle-fpqly' cent N-vinylimidazole in' polymeric form;based In 'genergdefromgwqto per ace-9t of the on the totalweight 'of'polymerized-monomers in b n in o i dnwit r m 8:p. x ia thejblende-d polymer;;

0 Per cent the n-d m P will "211A dyeableefiber forming-composition;coin- 1ude the P i- "prising a blendof from 70-t0;98 ne'reent'of' a The mended fiwn ger mltio polymer of at4lea'st 75 per"cent ofacrylonitrile ymht1fibe5 by ."conyemmna-l Wet rand ?dry and up: to 25 percent of anotherpelym'er'izable spinning method s After stretchingthefibersv -olefinicsmbnomen -and'from-tWo to SOpercentof il -ble ded e rr eili i mlyme -i develop h a polymer of at lea'st 30 per centof N-vinylimiw 'necessary orientation;in the fiber and the inr u t 1- e 1 acidental tensile Y, strength, and} thereafter heat lpizabletolefinfig 2 6 53;? 3mi m frvshrinkmg'm improve their msistgme melgvated' 3. ""Ardyeablefiber' iormihg composition comtemperature s Valuable generalipurposreifibers are lprising a 'blend of polyacrylonitrile and a copolymere-by tamed! me'r' of at least '30 per cent of N-vinylimid'az'ole Furt de offihle pfadfiilbfthig 'g l-with another'polymerizable olefinic' monomer, m setforth iw-mh respect-i9 i e Pl the gcomponents' of the=blend being so proporexamplesir Z 1 a. tion'ed' 'asto: provide from two to ften percent of j N-viriylimidazolein polymeric foimgbased on' 'tl'ie. mixture of 70 grams o'f'aorylonitrile and 70 total weight ofjpolymer'iz ed monomers-in ant:

'fl rams of N-vinylimiclazole was mixed with one H blended-"polymer; -5 l a -pe r cent byweig'ht of azodiisobuty-ronitrile,"and fiA-dyeable fiber-formingcomposition cemthe' re'siiltant nfi'ixture added overa'period 'of 1:2 "prising a'blend' of acopolyrner of'at least fl 5'per hours to 800 'grams of water containing' 'four "cent'oi acryloni'trile' and upZ'to'25 percent of grains of sodium stearate' and two grarn's'of' the -vinyl'acetateanda copolymer' of from 30 to 90 -s'o'diunisalt of iorm'aldehydecondense'd 'qiaphper c'ent'by W t of -v ylim da-zole and ten 'tlialenesulfonic'acidJ 'Ifhe reaction was maint6 70 p cent ofaclylonitrile, e p ts of 'ta'ined at 83 C.-througho'ut the polymer iza'tion. the blend being so proportioned as to provide After-ail of "the mo'nome'rsl hadbeen added" the f tw t en p r c nt-bfN vinyli idaz le in *m'ixtu e' was steam" distilled to removeunreacted "po ymeric form, based on the-total polymerized monomers. The -material was dr'iedat 70 C. monomersinthe blended polymer; 1 overnight and then dissolved'in N,N-dimethy1f *5. A dyeable fiber forming composition -comacetamide to form a 24 per cent solution? pri ing a blend f opo ym r 6 i r' cent'by I The resultant solution was thenble'nde'd} with 'Wei htofac'rylonitrile and three percent of vinyl an 18 per cent solutionofa -'polymer of-97 per fi 'fi 00p01ymr0f50peivcefit y' cent'of acrylonitrile and three'pe'r'cent vinyl f acryl'o itrile 'and ,fiope'r cent N-vin'ylimidacetate, also in N,N-dimethylacetamide. *suflim l s 'id op s'b e pron r ion d'that pient of' the vinyl acetate copolymer was added f two to t per cent of-the total monomer to yield a solution of a blended polymer of which polymeric OIm'l l o hcbpolymers is N -V iny1 "theN-vinylimidazole representedfifi per cent of mid o efi r 1 4 the solid polymer. The soluti'onso'p'repared was A dyeable fi folm'ilflg pos tion (50!!!- spun intofibers having a tenacity of 4.5fg./d.and rising'a bl nd f a 'cop' iym r of acr lonitrile an elongation of six per cent'and a boil'shrinkage and t pdly za'ble-olefinic 'monom'enand of 10.4 per cent; The fiber so prepared exhausted & 1 0 3 0f P l y ight of acrylo- "both two and ten per cent WooI'ScarIet dye'b'aths nitrile and 50 per cent of N -vinylimidazole,- said 1 cop'olymers beingso proportioned 'tha't 'from 'two to-tem er 'c'ent'of thertotal monomer mboiy- I a V i a. V "E: mric forminbo'th"copolyrners is N-vinylimid Using -the-procedure described in the preceding 'azole. 1 r Y 1: 'examplea: series- 0f blendswere prepared from 7. A dyeable fiber-forming" composition comlthe copolymer of 97 per cent by weight'of acryloprising a blend of a copolym'er of atileast 751m another polymerizable olefinic monomer, and a polymer of N-vinylimidazole, the components of copolymer of at least 30 per cent of N-vinylimidthe blend being so proportioned as to provide azole and up to '70 per cent of another polymerfrom 2 to 10 per cent N-vinylimidazole in polyizable o1efinicmonomer. meric form based on the total weight of poly- 8. A dyeable fiber-forming composition com- 5 merized monomers in the blended'polymer.

prising a blend of polyacrylonitrile and a copoly- I mer of 50 per cent by weight of acrylonitrile and ALFRED B, CRAIG,

50 per cent by weight of N-vinylimidazole, the EARL W. GLUESENKAMP,

components of the blend being so proportioned that from 2 to 10 per cent of the total monomer 10 REFERENCES CITED i Polymeric form in both components is The following references are of record in the lmidazolefile of this patent:,

9. A dyeable fiber-forming composition comprising a blend of a copolymerof at least '75 per UNITED STATES PATENTS cent of acrylonitrile and up to 25 per cent of 15 Number Name Date another polymeriza'ble olefinic monomer, and a ,5 ,863 Webb Oct.. 31, 1950 

2. A DYEABLE FIBER FORMING COMPOSITION COMPRISING A BLEND OF FROM 70 TO 98 PER CENT OF A POLYMER OF AT LEAST 75 PER CENT OF ACRYLONITRILE AND UP TO 25 PER CENT OF ANOTHER POLYMERIZABLE A POLYMER OF AT LEAST 30 PER CENT OF N-VINYLIMIDAZOLE AND UP TO 70 PER CENT OF ANOTHER POLYMERIZABLE OLEFINIC MONOMER. 